CN1711232A - Continuous process for producing pseudoionones and ionones - Google Patents

Continuous process for producing pseudoionones and ionones Download PDF

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CN1711232A
CN1711232A CNA2003801028095A CN200380102809A CN1711232A CN 1711232 A CN1711232 A CN 1711232A CN A2003801028095 A CNA2003801028095 A CN A2003801028095A CN 200380102809 A CN200380102809 A CN 200380102809A CN 1711232 A CN1711232 A CN 1711232A
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ketone
ionone
reaction
pseudo
aldehyde
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CN1310863C (en
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W·多布勒
N·巴尔
K·布罗依尔
A·金德勒
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • Organic Chemistry (AREA)
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Abstract

The invention relates to a continuous process for producing pseudoionones of general formulas (I) and (I') as well as isomers thereof, whereby: R1 represents CH3 or (a); R2 and R3 represent hydrogen, CH3 or C2H5, and; R4 an d R5 represent hydrogen or CH3. These pseudoionones are produced by reacting an aldehyde of formula (II) with an excess of a ketone of general formula (III) , whereby R1, R2 and R3 have the aforementioned meanings, in the presence of water and alkali hydroxide at an increased temperature and in a homogeneous solution. The inventive process is characterized in that: a) the intermixing of the homogeneous solution consisting of aldehyde, ketone and aqueous alkali lye occurs at a temperature ranging from 10 to 120 ~C; b) the undissolved water and alkali hydroxide contained in the reaction mixture are subsequently separated out; c) while avoiding back mixing, the homogeneous reaction mixtu re is then guided through a reactor, which permits a residence time ranging fro m 2 to 300 minutes, at a temperature that is 10 to 120 ~C higher than the boiling point of the lowest-boiling component and under a vapor pressure p ranging from 106 to 107 Pa; d) the reaction mixture is cooled by expansion; e) ketone is removed from the reaction mixture using vapor flowing in the opposite direction and; f) the raw product is dried and rid from excessive aldehyde and secondary components via a rectification column.

Description

The continuous preparation method of pseudo-ionone and ionone
The present invention relates to be used to prepare pseudo-ionone and selectively it is cyclized into the continuation method of ionone subsequently.The method that preferably is used to be prepared as follows compound is 6-methyl heptan-3 for example, 5-diene-2-ketone, pseudo-ionone, methyl pseudo-ionone, dimethyl pseudo-ionone, pseudoirone, methyl pseudoirone and dimethyl pseudoirone and cyclisation product thereof, α-, β-and γ-ionone, α-, β-and γ-methyl ionone (n-form, iso-form or mixture) and homologue.These materials have huge economic implications as spices and spices intermediate.Pseudo-ionone self is again the important intermediate that is used to prepare vitamin-E and A and carotenoid.β-ionone is the important intermediate that is used to prepare vitamin A and carotenoid.
For prepare pseudo-ionone by citral for, known many methods.
PL 147748 described by in 56 ℃ on alkaline ion exchanger condensation citral and acetone prepare the method for ionone.According to this method, acetone and citral were intermittently stirred 5 hours with described catalyzer in flask.The shortcoming of this method is low-down space-time yield.
DE-A 33 19430 instructed by in tubular reactor in 100～280 ℃, 10～60 crust in the presence of the hydrogen on the blended metal catalyst condensation methyl ketone and unsaturated aldehyde prepare the method for higher ketone.
At US 4,874, described in 900 by using LiOH citral and acetone to be reacted the method for preparing pseudo-ionone as catalyzer.According to this method, under-20～240 ℃ temperature intermittently or react continuously.Regulate pressure so that described reaction mixture keeps liquid phase under suitable temperature.Under the situation of periodical operation, reaction stirred and leach catalyzer when finishing in still when reacting, yet, in continuous mode, with the reactant pumping that is pre-mixed tower by catalyst filling.In both cases, after finishing, reaction uses CO 2The neutralization reaction mixture also leaches excessive ketone.In this method, be under 20 the condition in the mol ratio of acetone and citral, obtain the yield of 89.5% citral.These low yields can not be satisfactory for plant-scale method.
DE-A 31 14071 has described by at elevated temperatures aldehyde and excessive reactive ketone being prepared the method for pseudo-ionone.
Prior art also discloses many methods that pseudo-ionone is cyclized into ionone subsequently that are used for.For example, be known that with acid for example the vitriol oil or phosphoric acid cyclisation pseudo-ionone obtain α-and the mixture of β-ionone on.The ratio of the formation amount of these compounds depends on the condition that reaction takes place to a great extent.
Under the situation with vitriol oil cyclisation, wherein the cyclic action very exothermic in order to prevent hot localised points, is importantly very rapidly removed reaction heat.For this purpose, in known method, add thinner to reaction mixture.
If one object of the present invention is to develop a kind of be used to prepare pseudo-ionone and the suitable method that is cyclized into corresponding ionone subsequently, it compared with prior art needs less raw material and becomes more product with every part of raw material family planning.
1. according to the present invention, described purpose is used to prepare the pseudo-ionone of general formula I or I ' and the continuation method of isomer realizes by providing a kind of,
Or
R wherein 1For
CH 3Or
Figure A20038010280900063
R 2, R 3Hydrogen, CH respectively do for oneself 3Or C 2H 5,
R 4, R 5Hydrogen or CH respectively do for oneself 3,
This method is by the aldehyde with formula (II)
Ketone with excessive general formula (III)
In homogeneous solution, under the temperature that raises, in the presence of water and alkali metal hydroxide, react, wherein R 1, R 2And R 3Definition as mentioned separately, described method comprises
A) homogeneous solution of mixed aldehyde, ketone and aqueous alkali metal hydroxide under 10～120 ℃ temperature, then
B) remove water and the alkali metal hydroxide that is not dissolved in described reaction mixture as yet,
C) subsequently in the temperature and 10 of 10～120 ℃ of the boiling points that is higher than the minimum boiling point component 6～10 7The vapour pressure p of Pa down with described uniform reaction mixture when avoiding back-mixing by the reactor of 2～300 minute residence time can be provided,
D) under reduced pressure cool off described reaction mixture,
E) with reflux type with steam from described reaction mixture, remove described ketone and
F) dry raw product and therefrom remove excessive aldehyde and secondary component with rectifying tower.
Preferably use method of the present invention to prepare 6-methyl heptan-3,5-diene-2-ketone, pseudo-ionone, methyl pseudo-ionone, dimethyl pseudo-ionone, pseudoirone, methyl pseudoirone and dimethyl pseudoirone and isomer thereof.
Used aldehyde is preferably citral, geranial and 2 according to the present invention, 6-dimethyl octanal, and any straight chain or branching, saturated or undersaturated aldehyde with 1～10 carbon atom, and used ketone is preferably acetone, 2-butanone or 2-or propione.
Aqueous alkali metal hydroxide refers to the aqueous solution of potassium hydroxide, sodium hydroxide or lithium hydroxide, but preferred sodium hydroxide solution.The concentration of used alkali metal hydroxide is 0.005～50 weight %, preferred 1～15 weight %.
Described isomer refers to all possible positional isomers or the double bond isomer of described pseudo-ionone or ionone.
In the method for the present invention, under 10～120 ℃, preferably be lower than only in the uniform mixture of described aldehyde, ketone and water reactant, add its amount under 50 ℃ the temperature can be at the alkali hydroxide soln that mixes the back uniform dissolution closely.Remove isolating any water and alkali metal hydroxide, afterwards in the temperature and 10 of 10～120 ℃ of the boiling points that is higher than the minimum boiling point component 6～10 7(wherein p is the vapour pressure of described reaction mixture under temperature of reaction) avoiding in the back-mixing described uniform reaction mixture by the reactor of 2～300 minutes, preferred 5～30 minute residence time can be provided under the Pa pressure p.By the described reaction mixture of decompression cooling, a part of during this period described excessive ketone evaporation also can infeed recirculation with it, described ketone is removed from this reaction mixture with steam with reflux type then, described steam comprises the volatile acid of capacity with the described catalyzer alkali that neutralizes, and obtains pH value 4～9.Subsequently, dry raw product and with rectifying tower, preferably remove excessive aldehyde and secondary component with partition-wall column, for example disclosed among DE-A 3302525 or the EP-A 804951.
The present invention further provides the continuation method that is used to prepare general formula (IV), (V) and ionone (VI) and isomer thereof, it comprises that the pseudo-ionone that will obtain by the inventive method changes into the ionone of general formula (IV)～(VI)
Figure A20038010280900081
??
Figure A20038010280900082
??
Alpha-isomer β-isomer γ-isomer
(IV)?????????????????????????????(V)?????????????????????????????(VI)。
Surprisingly, when in described reactor, under being lower than technological temperature, but the mixture of ketone and aldehyde only being mixed with the alkali hydroxide soln of its amount uniform dissolution, can be suppressed at the formation of in the heterogeneous catalyst by alkali metal hydroxide, especially handling the secondary and degradation production that occurs as side reaction in the described reaction mixture, and in tubular reactor under the autogenous pressure under further blended condition the feasible temperature of reaction that reaches hope with the saturated described uniform mixture of alkali metal hydroxide aqueous solution.
Advantageously remove not being dissolved in as yet in the described mixture and therefore excessive any alkali hydroxide soln of appearance in the ingress of described reactor.This can or incorporate in the separator of described reactor bottom and realize at the additional separator in described reactor upstream.Equally advantageously can be metered in the described reaction mixture and from the ketone for the treatment of recirculation, remove excessive water, make described reaction mixture dehydration and the alkali metal hydroxide of aequum is dissolved in the described reaction mixture like this by alkali hydroxide soln with high density (promptly about 10～50%, preferred 35～45%).
In order to realize the optimal yield based on used aldehyde, described reaction is carried out with 5～50 times, preferred 20～25 times of molar excess ketone.In 10 7～10 9Remove unconverted ketone fraction under the pressure of mPaabs in the downstream of reaction zone and with it for being back in the fresh ketone of described synthetic.
Surprisingly, the same particularly important of the water content of described aldehyde-alcohol/ketone mixtures.But this has obviously determined the amount of the alkali metal hydroxide of uniform dissolution in described aldehyde-alcohol/ketone mixtures.Water content in described aldehyde-alcohol/ketone mixtures should be 1～15 weight %.The amount of described dissolved alkali metal hydroxide has determined transformation efficiency again, and can influence the appearance of undesirable by product.This is that favourable this fact conforms to remove excess base in the reactor upstream.Contrast with prior art, because water content causes that because of reaction water increases alkali metal hydroxide further is dissolved in the described reaction mixture, thisly further be dissolved in this stage and can promote the formation of by product when this can prevent near reaction end.The latter especially has material impact and can reduce yield under the situation of the unsaturated aldehyde (for example citral) of sensitivity.
Described water is advantageously by being in that part in the described ketone component infeeds in this technology and producing in the downstream of described reactor by described reaction mixture being carried out steam gas is carried.Economic implications is that this makes and can removes described excessive ketone with technical complexity and the low mode of energy intensity, because the complicated drying before the recirculation becomes unnecessary.As selection, can carry out with the anhydrous mixture of aldehyde and ketone equally and mixing in required water (about 1～15 weight %) by using very rare alkali hydroxide soln.On the contrary, when sneaking into spissated alkali hydroxide soln, can use the mixture of very high aldehyde of water content and ketone.In this case, in order to prevent uncontrollably to begin described reaction, need lower mixing temperature.Simultaneously, the consumption of alkali metal hydroxide increases, and enters in the described organic phase because it only partly shifts.It partly makes described aldehyde-alcohol/ketone mixtures dehydration and has to be removed and handle.
In tubular reactor, under autogenous pressure, heat described uniform reaction soln, and regulate the temperature of reaction under the given residence time so that the transformation efficiency of described aldehyde component is 60～98%, preferred 85～95%, remove unconverted aldehyde and its recirculation is entered in the described reaction.The size of described tubular reactor should make that described mean residence time is 2～300 minutes, preferred 5～30 minutes, causes like this to have very small amount of back-mixing.Higher transformation efficiency need disproportionately improve described temperature of reaction, and this can promote by product to form.Lower transformation efficiency makes that lower temperature of reaction becomes possibility, can suppress the appearance of described by product like this, but the recycle stream of described ketone and aldehyde increases and therefore cause the energy requirement of this method to increase.
In the described tubular reactor, must reduce back-mixing to greatest extent.This can realize or realize by the laminar flow internals of any kind to be avoided turbulent flow by enough big reactor diameter.This is surprising and opposite with prior art, prior art for example among the DE-A 31 14 071 design of tubular reactor must make and under reaction conditions, have enough turbulent flows.
Described reaction mixture is decompressed to standard pressure, and it cools off by evaporating a part of excessive ketone during this period.The steam of the volatile acid by wherein having added equimolar amount in counter-current tower and residual ketone is removed, described during this period catalyzer alkali is neutralized by described condensation product and dilutes.The use of tower packing can guarantee cat head except ketone and water, also obtain its amount unconspicuous other product, and advantageously regulate this tower quantity of reflux so that described ketone remove with the water of aequum.The consumption of acid advantageously makes and obtains to help the further pH value 4～9 of processing in this.After removing described water, by being heated and spurting in the flasher under the pressure that remains on reduction and dry described raw product.Therefrom, described mixture is transferred to rectifying tower, wherein the described beta-unsaturated ketone of purifying and is removed unconverted aldehyde removing impurity wherein under the pressure that reduces, and therefrom it is infeeded recirculation.Described recirculation is advantageously carried out in partition-wall column, and described in EP-A 804 951, it preferably has 2 side line extraction so that obtain two main fractions (product and aldehyde) with enough purity simultaneously in a step.
When adopting citral as described aldehyde component and 2-butanone during as described ketone component, aforesaid method has very special importance.But form the typical mixture of 70～97%n-methyl pseudo-ionone and 3～30%iso-methyl pseudo-ionone and the typical mixture that cyclisation produces the methyl ionone.The methyl ionone exists with the isomer ratio that alters a great deal.It is used for manufacture spices in a large number by perfume industry separately.Because the fragrance characteristic of each isomer ratio is slightly different, in a single day the reproducibility of isomer ratio is most important when therefore using.
In order to prepare corresponding ionone, with the mixture of resulting pseudo-ionone and highly spissated (promptly about 50～about 98%) sulfuric acid be under the reaction conditions inert thinner in the presence of react, more advantageously as described in the DE 196 19 557.Different with it is, when residence time of keeping＞10 seconds between cyclisation and the hydrolysis,＜20 ℃ cyclisation temperature and＜90% sulfuric acid concentration are favourable.For the situation of methyl ionone, in about 25 ℃ under about 2 minutes residence time about 89% sulfuric acid concentration be favourable, almost all obtain β-isomer under this situation, and α-n-and γ-n-methyl ionone is suppressed to about 1%.For the situation of pseudo-ionone, form almost all β-ionones with 89% sulfuric acid with high yield, and α-Zi Luotong and γ-ionone are only removed from cat head in described purifying distillation difficulty in 1% scope and not.
The following example describes the present invention in detail, but does not limit it.
Embodiment 1
The preparation of pseudo-ionone
Citral (2.43kmol/h), the recirculation citral of about 26kg/h, moisture 95% acetone of 3800kg/h and 5% aqueous NaOH of 30kg/h of mixing 370kg/h.Form uniform solution like this, it is passed through phase separator as preventive measures.When water content or NaOH content were higher than prescribed value, water can separate and it must be separated after mixing step.Heat described mixture to 108 ℃ and pumping by 160 riser formula reactors.Reaction heat further is heated to about 112 ℃ with described mixture.Under about 2 minutes residence time, obtained about 93% transformation efficiency.
Reaction mixture from described tubular reactor is decompressed to standard pressure.During this period, distill out the acetone of about 2000l/h, and product solution is cooled to about 60 ℃.Subsequently, described mixture is removed residual acetone at reflux type with the steam of about 700kg/h.The acetate of capacity is joined in the described steam so that the pH value of neutralization of the sodium hydroxide solution in the described mixture and effusive aqueous mixture is 4～5.Described acetone recirculation is entered in this process.
Remove after the water, dry under about 100 ℃ and about 50 millibars and have a distillation purifying in the partition-wall column of 2 side line extraction.In bottom side line extraction place, obtain about 400kg/h purity and be 98% pseudo-ionone (GLC area %, all isomer total amounts).In top side line extraction place, obtain the citral (all isomer total amounts) of about 26kg/h and it is recirculated in the described process continuously.
Embodiment 2:
The methyl pseudo-ionone
Citral (0.72kmol/h), the recirculation citral (0.13kmol/h) of about 20kg/h, the moisture 82%2-butanone of 1800kg/h and 5% aqueous NaOH of about 20kg/h of mixing 110kg/h.Form uniform solution like this, it is passed through phase separator as preventive measures.When water content or NaOH content are higher than prescribed value, water can be after mixing separation and it must being separated.Heat described mixture to 136 ℃ and with the tubular reactor of its pumping by 160 liters.Reaction heat further is heated to about 138 ℃ with described mixture.In 4 minutes the residence time, obtain transformation efficiency based on citral about 82%.
Remove after the water, dry under about 100 ℃ and about 50 millibars and have a distillation purifying in the partition-wall column of 2 side line extraction.In bottom side line extraction place, obtain about 100kg/h purity and be 98% methyl pseudo-ionone (GLC area %, all isomer total amounts).In top side line extraction place, obtain the citral (all isomer total amounts) of about 20kg/h and it is recirculated in the described process continuously.
Obtain about n: iso=5: 1 isomer ratio.
Embodiment 3
The methyl pseudo-ionone
Citral (0.66kmol/h), the recirculation citral (0.16kmol/h) of about 25kg/h, the moisture 88%2-butanone of 2200l/h and 40% aqueous NaOH of about 120kg/h of mixing 100kg/h.Form two phase liquid like this, it is passed through phase separator.Remove the aqueous NaOH of about 120kg/h, heat the organic phase of about 2100kg/h down and 160 riser formula reactors are passed through in its pumping at 120 ℃.Reaction heat further is heated to about 132 ℃ with described mixture.Under 4 minutes the residence time, obtain transformation efficiency based on citral about 75%.
To be decompressed to standard pressure from the reaction mixture of described tubular reactor.During this period, distill out the 2-butanone of 1000l/h, and cooled product solution is to about 75 ℃.Subsequently, remove residual 2-butanone in the described mixture with reflux type with the steam of about 550kg/h.The acetate of capacity is joined in the described steam so that the pH of neutralization of the sodium hydroxide solution in the described mixture and effusive aqueous mixture is 4-5.
Excessive 2-butanone recirculation is got back in this process.
Remove after the water, dry under about 100 ℃ and about 50 millibars and have a distillation purifying in the partition-wall column of 2 side line extraction.In bottom side line extraction place, obtain about 100kg/h purity and be 98% methyl pseudo-ionone (GLC area %, all isomer total amounts).In top side line extraction place, obtain the citral (all isomer total amounts) of about 25kg/h and it is recirculated in the described process continuously.
Obtain about n: iso=8: 1 isomer ratio.
Embodiment 4
The methyl ionone
89% sulfuric acid of the about 140l/h methyl of uniform mixing pseudo-ionone, 400l/h hexane (being cooled to-8 ℃ in advance) and 200l/h continuously in reaction pump.Described reaction mixture spontaneously is heated to about 29 ℃, and it is cooled to about 26 ℃ and circulated about 2 minutes by pump in delay zone under this temperature, with about 600l/h water it is diluted in another reaction pump afterwards.Because the adding of water, described mixture heating up to about 47 ℃ and utilize downstream cooler hold it in＜45 ℃.After removing the high water of sulfuric acid content and after further water washing, remove described hexane with steam with reflux type.Hexane recirculation is got back in the described reaction.
Remove after the water, dry down and have a purifying in the partition-wall column of 2 side line extraction at about 50 millibars and 100 ℃.In main fraction (side pipe extraction 1), the β-n-methyl ionone content that obtains about 120l/h is 80～90% methyl ionone.
Following table has been listed a kind of typical case and has been formed 1):
α-iso-methyl ionone ??8.8％±1 The total amount of Iso-methyl ionone ??10.7％±1.6
β-iso-methyl ionone ??0.8％±0.1
γ-iso-methyl ionone ??1.1％±0.5
α-n-methyl ionone ??0.25％±0.1 The total amount of n-methyl ionone ??85.5％±1.8
β-n-methyl ionone ??85.0％±1.5
γ-n-methyl ionone ??0.3％±0.2
1)E-and Z-isomer detect together, and E-isomer comprises advantage.

Claims (10)

1. continuation method that is used to prepare pseudo-ionone and the isomer thereof of general formula I or I ',
Figure A2003801028090002C1
Or
Figure A2003801028090002C2
R wherein 1For
CH 3Or
Figure A2003801028090002C3
R 2, R 3Hydrogen, CH respectively do for oneself 3Or C 2H 5,
R 4, R 5Hydrogen or CH respectively do for oneself 3,
This method is by the aldehyde with formula (II)
Figure A2003801028090002C4
Ketone with excessive general formula (III)
Figure A2003801028090002C5
In homogeneous solution, under the temperature that raises, in the presence of water and alkali metal hydroxide, react, wherein R 1, R 2And R 3Definition as mentioned separately, described method comprises
A) homogeneous solution of mixed aldehyde, ketone and aqueous alkali metal hydroxide under 10～120 ℃ temperature, then
B) remove water and the alkali metal hydroxide that is not dissolved in described reaction mixture as yet,
C) subsequently in the temperature and 10 of 10～120 ℃ of the boiling points that is higher than the minimum boiling point component 6～10 7The vapour pressure p of Pa down with described uniform reaction mixture when avoiding back-mixing by the reactor of 2～300 minute residence time can be provided,
D) under reduced pressure cool off described reaction mixture,
E) with reflux type with steam from described reaction mixture, remove described ketone and
F) dry raw product and therefrom remove excessive aldehyde and secondary component with rectifying tower.
2. add described general formula (III) ketone component according to the process of claim 1 wherein with 5～50 times of molar excess, and in the downstream of reaction zone in 10 7～5 * 10 8MPa AbsPressure under remove unconverted part and it be conducted to once more and be used for the fresh ketone of described synthetic.
3. according to the method for claim 1 or 2, wherein select the temperature of reaction under the given residence time, and remove unconverted aldehyde and it is recirculated in the described reaction so that the transformation efficiency of described aldehyde component is 60～98%.
4. according to the method for claim 1～3, the water content that wherein is used for described formula (III) ketone of this reaction is 1～15 weight %.
5. according to the method for claim 1～4, the concentration that wherein is used for the alkali metal hydroxide of described reaction is 0.005～50 weight %, is preferably 5～10 weight %.
6. according to the method for claim 1～5, wherein said method is used to prepare R 2Or R 3Be pseudo-ionone and the isomer thereof of the described formula I of methyl, the concentration that is used for the alkali metal hydroxide of described reaction is 10～50 weight %, is preferably 35～45 weight %.
7. according to the method for claim 1～6, wherein used formula (III) ketone is basically by removing from described reaction and water content is that excessive formula (III) ketone of 1～15 weight % is formed, and it can be that aqueous described formula (III) ketone of 1～15 weight % replenishes with anhydrous described formula (III) ketone or water content.
8. according to the method for claim 1～7, wherein using R 2≠ H and R 3Under the situation of described general formula (III) reactive ketone of=H, obtain containing the product mixtures of 70～95%n-alkyl pseudo-ionone and 5～30% iso-alkyl pseudo-ionones
Iso-alkyl pseudo-ionone n-alkyl pseudo-ionone
。
9. continuation method that is used to prepare general formula (IV), (V) and ionone (VI) and isomer thereof, it comprises the pseudo-ionone reaction that will obtain according to claim 1～8, thereby to keep n-form (R according to Claim 8 2=H, R 3=alkyl) with iso-form (R 2=alkyl, R 3=H) form of ratio obtains the ionone of described general formula (IV)～(VI)
Figure A2003801028090004C2
Alpha-isomer β-isomer γ-isomer
(IV)???????????????????????????????????????(V)?????????????????????????????????????????????(VI)。
10. according to the method for claim 9, wherein will according to the pseudo-ionone of claim 1～8 gained and highly spissated sulfuric acid be under the described reaction conditions inert thinner in the presence of reaction to obtain ionone, described temperature of reaction is that the residence time between 0～20 ℃ and cyclisation and the hydrolysis is 10～300 seconds, preferred 120 seconds.
CNB2003801028095A 2002-11-07 2003-10-28 Continuous process for producing pseudoionones and ionones Expired - Lifetime CN1310863C (en)

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CN101781183B (en) * 2010-01-15 2012-08-22 绍兴文理学院 Preparation method of beta-ionone
CN101781182B (en) * 2010-01-15 2012-09-05 绍兴文理学院 Preparation method for jointly preparing beta-ionone
CN103044223A (en) * 2012-12-28 2013-04-17 安徽丰原发酵技术工程研究有限公司 Method for continuously preparing pseudo ionone of vitamin A intermediate
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CN113166018A (en) * 2018-11-13 2021-07-23 巴斯夫欧洲公司 Apparatus and method for preparing pseudoionone and hydroxy pseudoionone
CN111825538A (en) * 2020-07-13 2020-10-27 万华化学集团股份有限公司 Method for continuously producing pseudo ionone
CN111825538B (en) * 2020-07-13 2022-08-05 万华化学集团股份有限公司 Method for continuously producing pseudo ionone
CN111909017A (en) * 2020-08-06 2020-11-10 上海应用技术大学 Pseudo ionone preparation method for improving reaction rate and conversion rate

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